Production of alkyl substituted aryl hydrocarbons



:25 carbon material of the desired carbon content or P hydrocarbon m iis first chiorinatcd 25 to'i catalyze the splitting of the monochloridesj 55 the chlorides preparatory to the subsequent step conclusion'cf thecondensation reaction, com- 55 I Patented F b, 2%), 1937- 7 2,072,06L

' UNITED STATES PATENT OFFICE PRODUCTION or 2mm suns'r'n'cm ARYLHYDBOCARBONS Charles A} Thomas, Wayne, Pa., asslgnorto The 'SharplesSolvents Corporation, Philadelphia,- Pa., a. corporation of Delaware 4No" Drawing. Application August 28,1933, Serial No. 687,245

o 4 Claims. (or. 260-168) I The present invention relatestothealkylation' "in which the chlorides are condensedwith the I of arylhydrocarbonsby. the substitution of alkyl aryl y 08 radicals ofrelativelyhigh carbon content for The higher molecular'weight chlorideswhichnuclear hydrogen of such hydrocarbons.- It is are to be used in thecondensation reaction arei re'particularly concerned with the productiono close n boiling a ce. to the hydr c n of alkyl substituted arylhydrocarbons having immw i h y, a d i d a t ey can on from eight tothirty carbon atoms in the alkyl be separated from the unr actedhydrocarbonsside chain. It is the object oi the invention'to with greatty-"f In some instances 01 0 110- p i produce compounds of this ty e bya commerrination or mixtures of isom ric par -fin y cially feasibleprocess afiording a high yield oi; a o s t es a es actually ve eachother, 10 thejiesired compound by arelatively inexpensive andin u hnstam a 'a fl 18 3' procedure. Important economies are attained in tremelydifiicult. ,A fu h r id fii ulty is ncoune- I the performance of theprocess by reason 01 th d y r on'cfthe fact t h large P 0P0 fact-that itmayb performed i r lati l i tion 01' thesealkyl chlorides are decomposedwhen pensive apparatus apdzbecause' the unused prody are e d'i l a n aAttempts 15 nets are recovered in aform which makes'possiatdistillationcin such appar tus c rd ngly e ble their reuse in arepetition of theprocess; 1 $1111; n d sired splitting of, much of thechlo- I Theprocess of-the invention is based iundaa e ma ial 'to P ecleflns d ydro-- mentally upon'the well-known Friedel and Crafts l ic irn c d cv littin in such Y reaction by which alkyl chlorides arecondensed, an opera mit is necessary that the distilla 20 y withsubstituted or unsubstituted aryl hydrocare nducted in apparatusma'de ofglass or other Lions in the presence of anhydrous aiuminun expensive net material which does not ct a chloride or other equivalent catalyst. 3It involves a 8 f a-lystto Cause h splitting 0! F 8 c oriaesthe initial.step of chlorinating parafiin hydron he practice of the pr nt inventionrange 1 and the. condensation of chlorinated hy- 9 Produce m x re ofhydrocarbons and chlodrocarbon material with an aryl compound in the ag-"E g c i a ici i f t y fil n esenceof, a catal st. Y P Orme 3 P 11ggaseous c 0113116" ji number of diific ulties are encountered inc-om; 8ui o f fl n h s chlorinanection with attempts to perform such-:a series;j i c cn is i continued long' before com-- .39

of operations in the production otsalkyl chlorides him-"191011 Of a culach 9 0 9 r of high molecular weight and the subsequent sep- W h e ydocarbon under treatment. This 1 aratlon ojf'mono-chlorides so .formedh'om-unkgl s fh l a h fi 5 22 31 1 i ilgl 'gg reacted paraflinhydrocarbons and poly-chlorides. 0 8 5S 9 i 0 ma The performance of thechlorination operation 'fl that. dBc0mR0$itih Oi q f d 35 by a procedureinvolving the conversion '01 the E e leactmni a subsequent l/' r i 01Poly" major portion of the h drocarbon into chlorides 2333 31 n z g szfi g ig g cg giei fis necessarily resultsv in e production or a large vY proportion of undesired poly-chlorides. Even'in production of any 43 Pcasesgin which chlorination is terminated long beqc s v {ore amolecularproportiohIQf chlorine has com= fia 538? 2;2 22

bined-with'the hyqmcarbon'agreat deal of entire mixed-ch l rides and ha'r:flin y desired formation of polychloride material ocdmcrbbns is mi 71 I xed -W1th the aryl hydrocarbon is??? when the react a 'with whichitis to'becpndensed. rt'isitobe- 45 apparatus. apparatus tending notedthat no attempt at separation of r I formed to produce oleflns andhydrochloric acid,.. gg gggzitgggm gf g ggag fii V as olefins so formedhave atendency to promptly A alkyljhydmcarbons and alkyljmondes is nexti, m with more m P Pmduce undesired stlrred during the addition of a.suflicient quantity 5o dichlorides. If the chlorination operation isnotoiranhydmus aluminum chlonge or other-equlwp n carriedtosubstantial-completion, seri u F 9 1 'lent catalyst to effectcondensationofthe alkyl' lems 0t distillatiom are also encouhtered insepachlorides with th hiy]; hydrocarbon m m-E1. raiicn un acted pa aflinhydro arbons .from sinc with the Friedeiandcrafts reaction. .At the wplex is decomposed with dilute hydrochloric acid or cold water and themixture distilled until the unused hydrocarbon is recovered, and furtherdistilled to effect separation of the desired alkyl substituted arylhydrocarbon from the residue.

In a typical example of the practice of the invention, the followingprocedure was adopted:

1000 grams of mixed parafiin hydrocarbon material consisting principallyof dodecane was partially chlorinated by bubbling chlorine through thematerial until it had gained 70 grams in weight; i. e., untilapproximately 35% of the hydrocarbons had been converted tomonochlorides. 3 liters of benzene were added to the mixture ofchlorides and paraffin hydrocarbons and the mixture was stirred duringthe addition of 200 grams of anhydrous aluminum chloride. After one-halfhour the complex was decomposed by the addition of a small amount ofdilute hydrochloric acid and the mixture was steam distilled until allof the unused benzene had been recovered. The residue was then vacuumdistilled and yielded 660 grams of hydrocarbon material.

Tests with bromine water indicated that this hydrocarbon was saturatedand could hence be used in. a second chlorination and condensation inconnection with a repetition of the process.-

238 grams of material having a boiling range .from 185-210 C. at 25 mm.pressure and consisting principally of lauryl benzene was recovered. Aresidue of 98 grams which is believed to have comprised principallydilauryl benzene, was obtained.

It Will be noted that the practice of the inven-- tion in accordancewith the above described procedure involves avoidance of the; loss ofvaluable paraffin hydrocarbon and other difficulties incident to theformation of dichlorides such as would be encountered in connection withattempts to effect more complete chlorination of the hydrocarbon mixtureor chlorination in metal apparatus and that the use of the entiremixture of chlorides and paraflin hydrocarbons in the subsequent step ofcondensation with the aryl hydrocarbon obviates the diificult problemsof fractionation referred to above. While great difficulty would beencountered in attempts to Sep arate the unreacted paraflin hydrocarbonmaterial from corresponding chlorides, the separation of this materialfrom the alkyl substituted aryl compounds by distillation is notdifiicult, as these last-mentioned compounds have boiling ranges muchhigher than the parafllns or chlorides used in the condensationreaction.

Modifications will be obvious to those skilled in the art and I do nottherefore wish to be limited except by 11319 590138 of my subioined'claims. The chlorination may, for example, be carried out in thevaporphase provided a substantial molecular excess of hydrocarbon isused. In the interpreta tion of the claims, I wish it to be understoodthat the term aryl compound is intended to include not onlyunsubstituted aryl hydrocarbons, such' alkyl poly-chlorides, mixing themixed mass of alkyl chloride and paraflin hydrocarbon with the arylcompound which is to form the aryl radical of the desired derivative,condensing the alkyl chloride of the mixture with the aryl compound andthereafter separating the uncondensed material from thedesiredderivative by distillation to obtain amass of the desired alkylderivative substantially free of paraflin hydrocarbon and chicrinederivatives.

2. The method of producing a mass ofv material comprising essentially amono allgvl derivative of an aryl compound containing from eight totwenty carbon atoms in its alkyl radical which comprises chlorinatingparaflin hydrocarbon material corresponding in carbon content to thealkyl radical of the desired derivative to an extent sufficient toproduce a mixture of the paraflin hydrocarbon and the correspondingalkyl monochloride but insufficient to produce any substantial quantityof alkyl polychlorides, mixing the mixed mass of alkyl chloride andparafiin hydrocarbon with the aryl compound which is to form the arylradical rine derivatives.

3. The method of producing a mass of material comprisin'g essentially amono-alkyl derivative of an aryl compound which comprises chlorinatingparaflin hydrocarbon material corresponding in carbon content to thealkyl radical of the desired derivative to an extent suflicient toconvert a part but less than one-half of the material into thecorresponding alkyl mono-chloride while avoiding production of anysubstantial quantity of alkyl polychlorides, mixing the resultingchloride together with the unreacted hydrocarbon with the aryl compoundwhich is to form the aryl radical of the desired derivative, condensingthe alkyl chloride of the mixture with the aryl compound and thereafterseparating the uncondensed material from the desired derivative bydistillation to obtain a mass of the desired alkyl derivativesubstantially free of paraffin the corresponding alkyl mono-chloride butnot sufficient to produce any substantial quantity of alkylpoly-chlorides, mixing the resulting mass of alkyl chloride and parafiinhydrocarbon with the aryl compound which is to form the aryl radical ofthe desired derivative, condensing the alkyl chloride of the mixturewith the aryl compound and thereafter separating the uncondensedmatedial from the desired derivative by distillation to obtain a mass ofthe desired alkyl derivative substantially free of paraflin hydrocarbonand chlorine derivatives, said process being carried out whilemaintaining the reactants out of contact with materials, such as variousmetals, that cause the formation of undesirable compounds.

cmmrns A. THOMAS.

